CN100344699C - Polyamide acidic composition and polyimide/copper foil laminated material - Google Patents
Polyamide acidic composition and polyimide/copper foil laminated material Download PDFInfo
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- CN100344699C CN100344699C CNB2005101061060A CN200510106106A CN100344699C CN 100344699 C CN100344699 C CN 100344699C CN B2005101061060 A CNB2005101061060 A CN B2005101061060A CN 200510106106 A CN200510106106 A CN 200510106106A CN 100344699 C CN100344699 C CN 100344699C
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Abstract
The present invention relates to a polyamide acidic composition and a polyimide/copper foil laminated material, partically a polyamide acidic composition. A polyamide acidic composition and a polyimide/copper foil laminated material which is used for a flexible printed circuit board are provided. The present invention comprises polar non-protonic solvent and polyamide acidic molecules which are formed by the copolymerization of a plurality of diamine monomers and a plurality of bianhydride monomers, wherein the diamine monomers comprise at least one rigid diamine monomer and at least one soft diamine monomer, the bianhydride monomers comprise at least one rigid bianhydride monomer and at least one soft bianhydride monomer, the rigid diamine monomer is selected from p-phenylene diamine, the rigid bianhydride monomer is selected from tetracarboxylic bianhydride or pyromellitic dianhydride, the soft diamine monomer is selected from oxygen-diphenylamine or 4.4 ' bisphenol A diphenyl ether diamine, and the soft bianhydride monomer is selected from benzophenone-tetracarboxylic bianhydride or biphenyl anhydride sulfone. The polyimide/copper foil laminated material which is used for the flexible printed circuit board is provided with a copper foil and a polyimide layers, and the composition is coated on the copper foil.
Description
Technical field
The present invention relates to a kind of polyamic acid composition (polyamic acid composition), be meant a kind of polyamic acid composition that after heat treated, can form polyimide (polyimide) especially, and utilize the prepared polyimide/copper foil laminated material that can be applicable to flexible printed wiring board of said composition.
Background technology
Be applicable to dynamic binding owing to flexible printed wiring board is bent, and have the advantage of imitating the utilization electronic product, be used in the mobile communication of densification day by day, light littleization and high-effectization and portable electronic product etc. in recent years already.
Because in the making processes of flexible printed wiring board, existence imposes the etching supervisor to the polyimide laminate material, for taking the quality of printed circuit board (PCB) into account, so industry requires very harsh for the physical propertiess such as the plumbous thermotolerance of stripping strength, dimensional stability, tin, thermal expansivity and planeness of the essential polyimide/copper foil laminated material of flexible printed wiring board.The essential layered material of relevant flexible printed wiring board generally is to include a conductive layer based on Copper Foil, and one includes polyimide and must fit tightly dielectric layer on this Copper Foil.More early stage layered material more includes one and connects this conductive layer and dielectric layer, and is the knitting layer that resin is constituted with Resins, epoxy or acryl usually.But because the thermotolerance of knitting layer material is not good and the problem of significantly breathing also arranged with temperature change, therefore easily peel off between polyimide layer and knitting layer, so develop the double-deck polyimide laminate material that no glue formula gradually, because it does not comprise knitting layer, so form is comparatively frivolous, flexibility is also good, and to have exempted Resins, epoxy and acryl be the problem that resin is unfavorable for follow-up printed circuit board (PCB) high temperature preparation.
Yet, the existing double-deck polyimide laminate material of no glue formula of not having a knitting layer in the preparation, solvent is all very high in the employed reactant solution, after solvent is removed in baking, because its overall volume die-offs, and high temperature produces cyclocondensation dehydration reaction down, thereby easily cause undesirable warpage, easily peel off between polyimide layer and knitting layer on the other hand, so can't take into account tackiness and planeness usually.
Be by selecting specific diamines and two anhydride monomer kind in No. 238318 patents of TW, limit each monomeric usage ratio, and employing double-coating mode for cloth, preparing double-layer polyamide acid films, the composition difference of this two polyamic acids layer wherein, by further adding the monomer that contains the bismaleimides functional group at the 2nd layer, make the preferable tackiness of tool between the 1st layer of polyimide/copper foil laminated material of making and Copper Foil, and the 2nd layer also can have preferable dimensional stability, and meet heat and be difficult for warpage, though this material part solves the rerum natura problem, but still have shortcomings such as the 1st layer of easy warpage and the 2nd layer and the 1st interlayer tackiness be not good unavoidablely.
Avoid warpage issues by for example adding inorganic filling material such as silicon-dioxide in No. 538071 patents of TW, to promote the planeness of polyimide layer, yet, its shortcoming be because of inorganic filling material without dispersion, can make integral material too firm easily crisp, ductility is not good, moreover its light transmission is relatively poor, therefore when needing on the preparation process to carry out contraposition, when will causing contraposition, relatively poor light transmission can't differentiate the desired position accurately, and therefore undesirable.Similarly, TW I220901 patent also is to improve rerum natura by adding without the dispersive inorganic filling material, so can meet with similar problem.
Selecting two or more diamine monomer or two anhydride monomer for use is the prepared polyimide of start material, owing to can more apply in a flexible way in the collocation of former material, has become present trend.But planting two anhydride monomers with plural number kind diamines and plural number is that initiator is when preparing polyimide, the way of present industry, two patents are disclosed as described above, mostly be to prepare respectively earlier to contain two amine aqueous solutions that plural number is planted diamine monomer, and contain two anhydride solutions that plural number is planted pair anhydride monomers, again two solution mixed mutually, then make it carry out polyreaction to form polyamic acid solution, and bestow high temperature again after coating on the Copper Foil, carrying out inferior amidate action, and generate a polyimide layer.
Yet, this case the applicant discover, the polyimide that makes with this method is at random (random) because of the combination between plural number kind diamines and two acid anhydride, even if the various reaction conditionss of strict control, its every quality is still wayward, and particularly the polyimide layer appearance flatness is not good, and product yield fluctuation simultaneously is very big, make every cost such as manufacturing and qualitative control increase, so stay in grade degree difference also becomes the secret worry of business-like polyimide/copper foil laminated material at present.
Therefore, for having the high polyimide/copper foil laminated material of excellent planeness and connectivity and quality stability concurrently, be that relevant at present dealer institute desire is pursued.
Summary of the invention
The objective of the invention is at the flat appearance degree of existing polyimide layer not goodly, product quality fluctuation is big, and problems such as cost height provide a kind of polyamic acid composition.
Another object of the present invention provides a kind of prepared polyimide/copper foil laminated material that can be applicable to flexible printed wiring board of polyamic acid composition that utilizes.
In the said polyamic acid composition, each polyamic acid molecule is to be arranged alternately to engage with the dianhydrides monomer by diamines monomer to form, diamines monomer used in the present invention comprises Ursol D (p-phenylene diamine, PDA), oxygen-pentanoic (oxy-dianiline, ODA), and 4.4 ' dihydroxyphenyl propane phenyl ether diamines (and 2,2 '-bis[4-(4-aminophenoxy) phenyl] propane, BAPP), its structural formula is then as follows respectively:
Dianhydrides monomer used in the present invention comprises two acid anhydride (the biphenyl tetracarboxylicdianhydride of hexichol tetracarboxylic acid, BPDA), two acid anhydride (the pyromellitic dianhydride of pyromellitic acid, PMDA), two acid anhydride (the benzophenone-tetracarboxylic dianhydride of benzophenone-tetracarboxylic acid, BTDA), and two phthalic anhydride sulfones (3,3 ' 4,4 '-diphenylsulfone tetracarboxylic dianhydride, DSDA), its structural formula is as follows respectively:
This case applicant divides into monomer whose " rigid structure " and " flexible structure " two kinds according to the difference of phenyl ring space displacement ability in above-mentioned each monomer structure.Only have a phenyl ring person in the structural formula, for example PDA and PMDA, and have two and in the structural formula mutually with the phenyl ring persons of a singly-bound bond, for example BPDA is classified in " rigid structure ".And have in the structural formula two phenyl ring and between with a bridge joint group connectionist, for example ODA, BTDA, BAPP, DSDA, then be classified as " flexible structure ", the monomeric phenyl ring of flexible structure is partly partly compared compared with the monomeric phenyl ring of rigid structure, has bigger space displacement ability.
According to above-mentioned idea, this case applicant divides into monomer whose " rigidity diamines monomer ", " flexible diamines monomer ", " rigidity dianhydrides monomer " reaches " flexible dianhydrides monomer ".Further, the fragment with at least one " flexible diamines monomer " forms with at least one " flexible dianhydrides monomer " reaction is defined as one " soft segment ".
The said polyamic acid composition of the present invention comprises a polar aprotic solvent, and by the polyamic acid molecule of plural diamines monomer and plural dianhydrides monomer copolymerizable gained, at least one is that the rigidity diamines monomer is flexible diamines monomer with at least one in the said diamines monomer, at least one is that rigidity dianhydrides monomer is flexible dianhydrides monomer with at least one in the said dianhydrides monomer, said rigidity diamines monomer is selected from Ursol D (p-phenylene diamine, PDA), rigidity dianhydrides monomer is selected from two acid anhydride (the biphenyl tetracarboxylic dianhydride of hexichol tetracarboxylic acid, BPDA) or two acid anhydride (the pyromellitic dianhydride of pyromellitic acid, PMDA), flexible diamines monomer is selected from oxygen-pentanoic (oxy-dianiline, ODA) or 4.4 ' dihydroxyphenyl propane phenyl ether diamines (2,2 '-bis[4-(4-aminophenoxy) phenyl] propane, BAPP), said flexible dianhydrides monomer is selected from two acid anhydride (the benzophenone-tetracarboxylic dianhydride of benzophenone-tetracarboxylic acid, BTDA) or two phthalic anhydride sulfones (3,3 ' 4,4 '-diphenylsulfonetetracarboxylic dianhydride, DSDA); Wherein, being engaged a polyamic acid fragment that forms by at least one flexible diamines monomer with at least one flexible dianhydrides monomer is to be defined as a soft segment, and with respect to all total moles monomer that are used to constitute said composition, its total moles monomer proportion that is used to constitute all soft segment is not more than 10%.
Because the industry ubiquity has the puzzlement that polyimide/the copper foil laminated material quality of finished differs at present, for example at different preparations batch each polyimide laminate material that is obtained, good and bad irregular, poor quality is apart from very big, even if same preparation batch prepared each polyimide layer material, the such situation of also normal appearance.Analysis according to this case contriver, mix mutually with the solution that contains plural number kind diamine monomer gradually by the solution that directly will contain the two anhydride monomers of plural number, prepare polyamic acid, can make that diamine monomer is the stochastic distribution state with two anhydride monomers on the molecule, so partly distribution density is higher for certain that same monomer may be on molecule, partly distribution density is lower at other, therefore is difficult to accurately controlling performance.Particularly, for example going through high temperature after forming polyimide layer, the amount that " flexibility " structure exists is too much or too intensive, easily has fold to produce, and the shortcoming of poor flatness is arranged, and so will have a strong impact on subsequent preparation process, so should do one's utmost to avoid; In addition in the intensive fragment of " rigidity " structure, then can make this fragment present a firmer character, and then can reduce its flexibility, but haply, amount of " rigidity " structure and intensity are to the influence of flexibility and other quality, still in the acceptable scope of this industry.
Further, this case the applicant also find, amount by the control soft segment, be not more than 10% of its all total moles monomer that are used to constitute composition even be used to constitute the monomeric total mole number of all soft segment, make planeness and other every character of the follow-up polyimide layer that makes all can obtain a comparatively gratifying result by this, simultaneously, also make the quality of prepared polyimide laminate than tool stability.
Based on the deficiency of known technology, the present invention quotes above-mentioned rigidity and flexible structuring concept, improves the planeness of polyimide/copper foil laminated material and the stability of product quality.It is reported that the restriction of patent or technical literature announcement with " rigidity ", " flexibility " monomeric combination or soft segment total amount in the polyamic acid do not arranged in this field as yet, promote every character of polyimide/copper foil laminated material.
Polyamic acid composition of the present invention is to be different from the structure that monomer engages at random in the known polyamic acid molecule.And analytical test according to this case contriver, also confirm polyimide/copper foil laminated material of the present invention, except the light transmission height of its polyimide layer, flat appearance, other every product rerum natura also presents gratifying result, with regard to different batches, with same batch of each polyimide/copper foil laminated material that is obtained, more represented the consistence of every quality.
The flexible diamines monomer that is used to constitute the present composition is oxygen-pentanoic or 4.4 ' dihydroxyphenyl propane phenyl ether diamines; Optionally, the flexible diamines monomer in the polyamic acid molecule can be all oxygen-pentanoic, or be all 4.4 ' dihydroxyphenyl propane phenyl ether diamines, or both all exist.
The flexible dianhydrides monomer that is used to constitute the present composition is two acid anhydrides of benzophenone-tetracarboxylic acid or two phthalic anhydride sulfones; Optionally, the flexible dianhydrides monomer in the polyamic acid molecule can be all the two acid anhydrides of benzophenone-tetracarboxylic acid, or is all two phthalic anhydride sulfones, or both all exist.
Preferably, this polar aprotic solvent is to be selected from the group that is made of following: methyl arsenic pyrrolidone (N-Methylpyrrolidone, NMP), N, the N-N,N-DIMETHYLACETAMIDE (N, N-Dimethylacetamide, DMAc), N, dinethylformamide (N, N-Dimethyl formamide, at least a in DMF) is preferably methyl arsenic pyrrolidone.
Preferably, this soft segment is by the two anhydride monomers reactions of at least one oxygen-pentanoic monomer and at least one benzophenone-tetracarboxylic acid and get.
Preferably, the mole ratio of this rigidity diamines monomer and flexible diamines monomer is 1～5, and this flexibility dianhydrides monomer and the monomeric mole ratio of rigidity dianhydrides are 0.2～2.0, and the mole ratio of this dianhydrides monomer and diamines monomer is 0.98～1.02.
Preferably, polyamic acid composition of the present invention more comprises a laminar nano clay that is selected from the following group that constitutes: kaolinite, serpentine, talcum, montmorillonite (Smectites), vermiculite, mica sodium montmorillonite (Na
+-at least a in Montmorillonite), this laminar nano clay is preferably sodium montmorillonite (Na
+-Montmorillonite)
Preferably, by weight calculating, in the total solid content of said composition, the content of this laminar nano clay is 0.1～2wt%.
Preferably, the cationic exchange equivalent of this laminar nano clay is 50～200meq/100g.
Preferably, this laminar nano clay is through the modification agent intercalation processing, and has 5～10 ° diffraction peak angle (2 θ) value through the analysis of X-x-ray diffraction.
In addition, this case also provides a kind of good physical properties that can be applicable to multiple occasion that has, and can have quality consistency under mass production, is applicable to polyimide/copper foil laminated material that flexible printed wiring board is produced, and comprises:
One Copper Foil; And
One polyimide layer is to be coated on this Copper Foil by above-mentioned polyamic acid composition, and heating makes said composition carry out inferior amidation to form then.
Preferably, the plumbous thermotolerance of the tin of the polyimide layer of polyimide/copper foil laminated material of the present invention is more than 320 ℃; Preferably, through IPC-TM-650 Method 2.2.13, Method B test, the dimensional stability of this polyimide/copper foil laminated material is less than 0.1%; Preferably, through the test of IPC-TM-650 Method 2.2.4 method, the stripping strength of this polyimide/copper foil laminated material is not less than 0.8kgf/cm; Preferably, the thermal expansivity of this polyimide layer is 10～30ppm/ ℃.
Description of drawings
Fig. 1 is an X-ray diffraction analysis figure, and the clay once upgrading is described, and is added with this dispersion situation through a polyamic acid composition medium clay soil of upgrading clay.In Fig. 1, X-coordinate is diffraction peak angle (2 a θ value), and ordinate zou is an intensity.
Embodiment
Following examples will further be done detailed explanation to the present invention, and following examples are only as the usefulness of example of the present invention, but not in order to restriction protection scope of the present invention.
The test materials that following examples adopt is:
1, phenylenediamine (PDA): U.S. Chriskev corporate system.
2, the two acid anhydrides (BPDA) of benzene tetracarboxylic acid: U.S. Chriskev corporate system.
3, the two acid anhydrides (PMDA) of pyromellitic acid: U.S. Chriskev corporate system.
4 ,-and pentanoic (ODA): U.S. Chriskev corporate system.
5, the two acid anhydrides (BTDA) of benzophenone-tetracarboxylic acid: U.S. Chriskev corporate system.
6, basic arsenic pyrrolidone: U.S. Tedia corporate system.
7, sodium montmorillonite: Japanese Kunipa corporate system, name of an article polynite.
8, clay modification agent (dodecyl sulfonic acid sodium salt salt): Japanese TCI corporate system.
Comprise at following each embodiment and the comparative example performance test that prepared polyimide/the copper foil laminated material sample is carried out:
1, peel strength test: according to IPC-TM-650 Method 2.2.4, use tension tester (model is LLOYD-LRX, by the manufacturing of middle roc instrument company), each polyimide/copper foil laminated material sample that is obtained is tested.
2, thermotolerance test: according to IPC-TM-650 Method 2.2.13 Method B, at room temperature, each polyimide/copper foil laminated material sample is soaked in the pyritous molten state tinsel takes out after 10 seconds, measure the top temperature when polyimide layer is about to peel off this copper foil layer in each sample.
3, high humidity thermotolerance test: similar above-mentioned " heat-resisting test ", difference is, being soaked in before superalloy tests, each material sample is placed on a temperature is about 40 ℃, rh value is about under 80% the hot and humid environment and lasts 24h.
4, dimensional stabilizing property testing (shrinking percentage): utilize IPC-TM-650, method2.2.4, Method B measures, each polyimide/copper foil laminated material sample is immersed in one mixes being corroded and till the only surplus polyimide layer to copper foil layer in the etching solution of concentrated hydrochloric acid (volume ratio 1: 1), and measure the dimensional change ratio of the polyimide layer before and after the copper foil layer corrosion with the hydrogen peroxide of concentration 2.98%.
5, unit elongation test: the polyimide layer in polyimide/copper foil laminated material sample is peeled off on Copper Foil, be cut into wide rectangular of a 3mm, by aforesaid tension tester, this is rectangular for the 50mm/min back draft to set draw speed, observes the variation ratio of its stressed front and back length.
6, open strength test: with above-mentioned " unit elongation test " condition, test this rectangular pulling force maximum value of breaking moment.
7, thermal expansivity (CTE) test: with thermo-mechanical analysis instrument (TMA) (U.S. PerkinElmer corporate system, model is Diamond TMA), the polyimide layer of each polyimide/copper foil laminated material sample is peeled off, and carried out the thermal expansivity test respectively.
8, testing flatness: polyimide/copper foil laminated material sample is cut into the square sheet of 300mm * 250mm, and lie against on the smooth sheet glass, measure calculating mean value behind the height of four jiaos of institute's warpages of each thin slice.
9, clay dispersion property testing: at (A) laminar nano clay through the intercalation upgrading, and (B) add polyamic acid composition through intercalation upgrading laminar nano clay, utilize X-ray radiation instrument (Dutch Philips corporate system, model is Philips X pertpro M) carry out the clay dispersion property testing, and via Prague diffraction formula (as shown in the formula) calculate the interlamellar spacing of (A) and (B) laminar nano clay, to confirm its dispersion situation.
Prague diffraction formula: n. λ=2.d.sin θ
Wherein, n is the storehouse cycle life; λ is a lambda1-wavelength; D is an interlamellar spacing; 2 θ are diffraction peak angle.
Embodiment 1
I. almost there is not the preparation of the polyamic acid composition 1 of soft segment existence:
PDA (0.6mole), BTDA (0.4mole) and BPDA (0.2mole) are dissolved in NMP, then under 5 ℃ temperature, carry out polyreaction, and solid composition is the solution A of 20wt%.Because selected diamine monomer is all inflexible PDA monomer, therefore, in this solution A, there is not the soft segment of any polyamic acid to form.
Again ODA (0.4mole) and PMDA (0.4mole) being dissolved in NMP, and carrying out polyreaction under 5 ℃ temperature, is the solution B of 20wt% to obtain a solid composition.Because selected two anhydride monomers are all inflexible PMDA monomer, therefore, in this solution B, there is not the soft segment of any polyamic acid to form yet.
Then this solution A is mixed with solution B, forming a solid composition is 20wt%, and viscosity number is the above mixed solution of 5000cps, then continues to stir this mixed solution in the temperature below 5 ℃, and then obtains a polyamic acid composition 1 that contains plural polyamic acid molecule.
In A, B solution mixing process, because solution A and the viscosity of B own are very high, be positioned at the BTDA monomer of a polyamic acid molecular end, very low with the ODA monomer collision that is positioned at another polyamic acid molecular end probability of joining, the monomer molar number that soft segment contained that therefore may generate certainly will be less than 10%, and almost is bordering on 0%.
II. the preparation of polyimide/copper foil laminated material:
Polyamic acid composition 1 is coated a copper foil surface in the mode of slit die formula coating (slot die coating), and to place a temperature be 200 ℃ baking oven, last 3 minutes and carry out drying.Then transposition is gone into one and is abound with in the baking oven of nitrogen atmosphere, carries out the polyimide reaction under 400 ℃ temperature, lasts 30 minutes, and obtains one polyimide/copper foil laminated material 1.
Embodiment 2
I. almost there is not the preparation of the polyamic acid composition 2 of soft segment existence:
PDA (0.8mole), BTDA (0.4mole), BPDA (0.2mole) and PMDA (0.2mole) being dissolved in NMP, and carrying out polyreaction under 5 ℃ temperature, is the solution C of 20wt% to obtain a solid composition.Wherein, because selected diamine monomer all belongs to rigidity, so there is not the soft segment of any polyamic acid to form in the solution C.
Again ODA (0.2mole) and PMDA (0.2mole) being dissolved in NMP respectively, then carrying out polyreaction under 5 ℃ temperature, is the solution D of 20wt% to obtain a solid composition.Similarly, because selected two anhydride monomers are rigidity, so there is not the soft segment of any polyamic acid to form in the solution D.
Then this solution C is mixed with solution D, forming a solid content is 20wt%, and viscosity number is the above mixed solution of 5000cps, then continues to stir this mixed solution in the temperature below 5 ℃, to obtain a polyamic acid composition 2 that contains plural polyamic acid molecule.Be similar to the polyamic acid composition 1 of embodiment 1, in like manner also can infer, because solution C and the viscosity of D own are very high, be positioned at the BTDA monomer of a polyamic acid molecular end, very low with the ODA monomer collision that is positioned at another polyamic acid molecular end probability of joining, the monomer molar number that soft segment contained that therefore may generate certainly will be less than 10%, and almost is bordering on 0%.
II. the preparation of polyimide/copper foil laminated material 2:
This polyamic acid composition 2 is coated a copper foil surface, and carry out subsequent operations, and obtain one polyimide/copper foil laminated material 2 in the mode described in the embodiment 1.
I. contain of the preparation of soft segment ratio less than 10% polyamic acid composition 3:
PDA (0.9mole), BTDA (0.3mole), BPDA (0.2mole) and PMDA (0.4mole) being dissolved in NMP, and then carrying out polyreaction under the temperature below 5 ℃, is the solution E of 20wt% to obtain a solid composition.Wherein, owing to do not contain flexible diamine monomer, therefore in this solution E, there is not the soft segment of any polyamic acid to become.
Again ODA (0.1mole) and BTDA (0.1mole) being dissolved in NMP respectively, then carrying out polyreaction under the temperature below 5 ℃, is the solution F of 20wt% to obtain a solid composition; Wherein, because of used diamines and two anhydride monomers all belong to flexible structure, so all polyamic acids all belong to soft segment among the solution F.
Then this solution E is mixed with solution F, forming a solid content is more than the 20wt%, and viscosity number is the above mixed solution of 5000cps, is then continuing to stir this mixed solution below 5 ℃, and then is obtaining a polyamic acid composition 3.Because the total moles monomer of all flexible diamines and two acid anhydrides accounts for 10% of these all total moles monomer that are used to constitute mixed solution among the solution F, therefore, in composition 3, the monomer molar number that is used to constitute all soft segment can not surpass 10% of these all total moles monomer that are used to constitute composition 3.
II. the preparation of polyimide/copper foil laminated material 3:
This polyamic acid composition 3 is coated a copper foil surface, and carry out subsequent operations, and obtain one polyimide/copper foil laminated material 3 in the mode described in the embodiment 1.
Embodiment 4
I. almost there is not the preparation that there is and contains the polyamic acid composition 4 of laminar nano clay in soft segment:
Present embodiment is the laminar nano clay that adds in the process of embodiment 1 preparation polyamic acid composition 1 through upgrading, and makes a polyamic acid composition 4.
Present embodiment difference from Example 1 when preparation composition 4 only is that before PDA, ODA were dissolved in NMP respectively, the solid content (solid content) that adds respectively with respect to PDA or ODA earlier was the sodium montmorillonite of 1wt%.Wherein this sodium montmorillonite be by program as described below by upgrading: will add in the deionized water (weight ratio is 1: 100) without the sodium montmorillonite of upgrading,, last 1h 60 ℃ of following dispersed with stirring; Back adding dodecyl amine salt (with the weight ratio of sodium montmorillonite be 2: 5) and continue dispersed with stirring, last 3h; Be cooled to after the room temperature with filter paper filtering, and, remove unnecessary dodecyl amine salt by this with washed with de-ionized water filter residue 3 times; Then filter residue is placed a baking oven that is set in 80 ℃ to carry out drying, last 20h after can obtain loose granule shape material, be 50 μ m with these particulate materials with ball mill grinding to granular size again, (Cation Exchange Capacity CEC) is the sodium montmorillonite through upgrading of 50～200meq/100g so promptly to obtain the cationic exchange equivalent.
Respectively at (A) through the sodium montmorillonite of upgrading and (B) add the polyamic acid composition 4 that this sodium montmorillonite is arranged and disperse test, and obtain as shown in Figure 1 result respectively, its middle conductor A representative is through the test result of upgrading sodium montmorillonite, and line segment B represents the test result of sodium montmorillonite in this polyamic acid composition 4.Line segment A shows that its X-ray diffraction angle 2 θ values are about 5.1 °, converts and learns this sodium montmorillonite behind upgrading, and the interlamellar spacing of its salt deposit is about 1.75nm; And because line segment B does not have crest and occurs, the sodium montmorillonite through upgrading that susceptible of proof is added in polyamic acid composition has been gone stratification (exfoliated), is to be scattered in equably in this polyamic acid composition really therefore.
The ratio that the total moles monomer that is used to constitute all soft segment in the present embodiment accounts for these all monomer molar numbers that are used to constitute composition is identical with embodiment 1, is less than 10% and almost is bordering on 0%.
II. the preparation of polyimide/copper foil laminated material 4:
This polyamic acid composition 4 is coated a copper foil surface, and carry out subsequent operations, and obtain one polyimide/copper foil laminated material 4 in the mode described in the embodiment 1.
Comparative example
I. contain the preparation that the soft segment ratio surpasses 10% polyamic acid composition 5:
PDA (0.85mole), BPDA (0.2mole) and PMDA (0.65mole) being dissolved in NMP, then carrying out polyreaction under the temperature below 5 ℃, is the solution G of 20wt% with a solid composition; Owing to there is no and select any flexibility two amines or dianhydrides monomer for use, in this solution G, there is not any polyamic acid soft segment to form.
Again ODA (0.15mole) and BTDA (0.15mole) being dissolved in NMP, then carrying out polyreaction under the temperature below 5 ℃, is the Solution H of 20wt% to obtain a solid composition.
At last, G mixes with Solution H with this solution, and forming a solid content is more than the 20wt%, and viscosity number is the above mixed solution of 5000cps, then continues to stir this mixed solution under the temperature below 5 ℃, and then obtains a polyamic acid composition 5.Because the total moles monomer of all flexible diamines and two acid anhydrides accounts for 15% of these all total moles monomer that are used to constitute mixed solution in the Solution H, therefore, in composition 5, the total moles monomer that is used to constitute all soft segment surpasses 10% of these all total moles monomer that are used to constitute composition 3, and is 15%.
II. the preparation of polyimide/copper foil laminated material 5:
This polyamic acid composition 5 is coated a copper foil surface, and carry out subsequent operations, and obtain one polyimide/copper foil laminated material 5 in the mode described in the embodiment 1.
The The performance test results of each embodiment and comparative example is compared as follows:
With each polyimide/copper foil laminated material that each embodiment and comparative example obtained, carry out dimensional stabilizing property testing, thermotolerance test, the test of high humidity thermotolerance, peel strength test, thermal expansivity (CTE) test respectively, and testing flatness, the average result of testing 10 times is respectively listed in table 1, wherein, IPC one hurdle represents that the public affairs of each test event decide standard value.
Table 1
| Project | Unit | Embodiment 1 | Embodiment 2 | | Embodiment 4 | Comparative example | IPC | ||
| Value of thrust (stripping strength) | 90° | kg/cm | 1.20 | 1.25 | 1.24 | 1.18 | 1.23 | 0.7 | |
| Tin lead is heat-resisting | 25℃ | ℃ | 320℃ | 320℃ | 320℃ | 320℃ | 320℃ | 288℃ | |
| 40 ℃/85% (temperature/humidity) | ℃ | 320℃ | 320℃ | 320℃ | 320℃ | 320℃ | 288℃ | ||
| Dimensional stability (shrinking percentage) | After the etching | TD | ％ | 0.03 | 0.04 | 0.05 | 0.02 | 0.15 | 0.15 |
| MD | ％ | 0.05 | 0.05 | 0.06 | 0.03 | 0.17 | 0.15 | ||
| Unit elongation | After the etching | ％ | 42 | 34 | 32 | 28 | 31 | - | |
| Tensile strength | After the etching | Mpa | 254 | 223 | 244 | 284 | 221 | - | |
| CTE | TMA | ppm | 28 | 20 | 30 | 10 | 35 | - | |
| Planeness | 300×250 mm | mm | 0 | 0 | 0 | 0 | 55 | - | |
By the data of comparative example as can be known, when the monomeric total mole number that is used to constitute soft segment greater than all total moles monomer that are used to constitute composition 10% the time, made polyimide/copper foil laminated material promptly has tangible planeness problem (55mm), and the obvious variation of dimensional stability (＞0.15%), anti-, amount by soft segment is accurately controlled in each embodiment below 10% and can finds out, every character that layered material of the present invention had, the public affairs calibration standard that surpasses not only far away all sidedly more can meet the harsh requirement of present industry.Simultaneously, each embodiment is under this comparative example, and flat appearance degree, the light transmission of the polyimide layer that is obtained are all splendid, help the carrying out of subsequent preparation process.
In sum, in molecule in the polyimide layer if controlled " soft segment " and amount, and with its total amount (monomer content) control in all monomer content that are used to constitute polyamic acid composition 10% in the time, really can make polyimide/copper foil laminated material and this polyimide layer of gained, even if do not add inorganic filling material, just can improve the problem of warpage, planeness is quite good, can obtain high light transmittance simultaneously.Therefore, generally speaking, not only can reduce cost, also can obtain to have very satisfactory flatness, and in stripping strength, thermotolerance, dimensional stabilitys etc. all have the very polyimide/copper foil material of superior performance in nature, material of the present invention also has high-elongation simultaneously, high-tensile, and low thermal coefficient of expansion, can say so and have omnibearing character advantage, so presenting in its effect, outclassed in the past and sacrificed the known technology of other characteristic for pursuing part character, and the finished product stability height that is obtained, be to be a big advantage compared to other industry finished product.Therefore, proper amt proposed by the invention " soft segment " notion, can overcome the shortcoming of known technology really, provide industry another have omnibearing superior character, and the high polyimide/copper foil laminated material of stay in grade degree.
The above person of thought, it only is preferred embodiment of the present invention, when not limiting scope of the invention process with this, promptly the simple equivalent of being done according to the present patent application claim and invention description content generally changes and modifies, and all still belongs in the scope that patent of the present invention contains.
Embodiment 5
Similar to Example 1, its difference is ODA is changed to BAPP, and BTDA is changed to DSDA, and NMP is changed to DMF.
Similar to Example 1, its difference is ODA is changed to the mixture of ODA and BAPP, and BTDA is changed to the mixture of BTDA and DSDA, and NMP is changed to N,N-dimethylacetamide.
Embodiment 7
Similar to Example 1, its difference is BTDA is changed to the mixture of BTDA and DSDA, and NMP is changed to the mixture of N,N-dimethylacetamide and NMP.
Claims (9)
1, polyamic acid composition is characterized in that comprising:
One polar aprotic solvent; And
Polyamic acid molecule by plural diamines monomer and plural dianhydrides monomer copolymerizable gained, at least one is that the rigidity diamines monomer is flexible diamines monomer with at least one in the said diamines monomer, at least one is that rigidity dianhydrides monomer is flexible dianhydrides monomer with at least one in the said dianhydrides monomer, said rigidity diamines monomer is selected from Ursol D, rigidity dianhydrides monomer is selected from two acid anhydrides of hexichol tetracarboxylic acid or the two acid anhydrides of pyromellitic acid, flexible diamines monomer is selected from oxygen-pentanoic or 4.4, and ' dihydroxyphenyl propane phenyl ether diamines, said flexible dianhydrides monomer are selected from two acid anhydrides of benzophenone-tetracarboxylic acid or two phthalic anhydride sulfones;
Wherein, being engaged a polyamic acid fragment that forms by at least one flexible diamines monomer with at least one flexible dianhydrides monomer is to be defined as a soft segment, and with respect to all total moles monomer that are used to constitute said composition, its total moles monomer proportion that is used to constitute all soft segment is not more than 10%;
The mole ratio of rigidity diamines monomer and flexible diamines monomer is 1～5, and flexible dianhydrides monomer and the monomeric mole ratio of rigidity dianhydrides are 0.2～2.0, and the mole ratio of dianhydrides monomer and diamines monomer is 0.98～1.02.
2, polyamic acid composition as claimed in claim 1 is characterized in that said flexible diamines monomer is selected from oxygen-pentanoic, 4.4 ' at least a in the dihydroxyphenyl propane phenyl ether diamines.
3, polyamic acid composition as claimed in claim 1 is characterized in that said flexible dianhydrides monomer is selected from the two acid anhydrides of benzophenone-tetracarboxylic acid, at least a in the two phthalic anhydride sulfones.
4, polyamic acid composition as claimed in claim 1 is characterized in that said polar aprotic solvent is selected from methyl arsenic pyrrolidone, N,N-dimethylacetamide, N, at least a in the dinethylformamide.
5, polyamic acid composition as claimed in claim 1 is characterized in that soft segment is by the two anhydride monomers reactions of at least one oxygen-pentanoic monomer and at least one benzophenone-tetracarboxylic acid and get.
6, polyamic acid composition as claimed in claim 1, it is characterized in that said composition comprises the laminar nano clay, said laminar nano clay is selected from least a in kaolinite, serpentine, talcum, montmorillonite, vermiculite, mica, the sodium montmorillonite, by weight the total solid content that calculates in composition, the content of laminar nano clay is 0.1～2wt%.
7, polyamic acid composition as claimed in claim 6, the cationic exchange equivalent that it is characterized in that the laminar nano clay are 50 to 200meq/100g.
8,, it is characterized in that said laminar nano clay is through the modification agent intercalation processing, and have 5～10 ° diffraction peak angle through the analysis of X-x-ray diffraction as claim 6 or 7 described polyamic acid compositions.
9, polyamic acid composition as claimed in claim 1 is used for polyimide/copper foil laminated material that flexible printed wiring board is produced, and it is characterized in that comprising:
One Copper Foil; And
One polyimide compositions layer, polyamic acid composition is arranged on the Copper Foil.
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| CNB2005101061060A CN100344699C (en) | 2005-09-27 | 2005-09-27 | Polyamide acidic composition and polyimide/copper foil laminated material |
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| CNB2005101061060A CN100344699C (en) | 2005-09-27 | 2005-09-27 | Polyamide acidic composition and polyimide/copper foil laminated material |
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| KR101064816B1 (en) | 2009-04-03 | 2011-09-14 | 주식회사 두산 | Polyamic acid solution, polyimide resin and flexible metal clad laminate using the same |
| CN107056634A (en) * | 2015-03-04 | 2017-08-18 | 湖南工业大学 | It is a kind of new with the diamine monomer of function containing naphthalene structure of high flatness and its synthetic method and application |
| CN105601919B (en) * | 2016-01-12 | 2018-03-27 | 湖南工业大学 | A kind of polyimide nano-composite material containing naphthalene structure and its preparation method and application |
| CN105601920B (en) * | 2016-01-13 | 2018-08-17 | 湖南工业大学 | A kind of polyimide nano-composite material and its preparation method and application containing fluorenes or Fluorenone structure |
| CN111500065A (en) * | 2020-05-29 | 2020-08-07 | 浙江中科玖源新材料有限公司 | High-barrier polyimide film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166292A (en) * | 1991-10-29 | 1992-11-24 | E. I. Du Pont De Nemours And Company | Process for preparing a polyimide film with a preselected value for CTE |
| JPH0551453A (en) * | 1991-08-22 | 1993-03-02 | Kanegafuchi Chem Ind Co Ltd | Polyamic acid copolymer, polyimide copolymer consisting of the same copolymer and polyimide film and production thereof |
| JP2004087548A (en) * | 2002-08-23 | 2004-03-18 | Kanegafuchi Chem Ind Co Ltd | Method for manufacturing printed wiring board |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0551453A (en) * | 1991-08-22 | 1993-03-02 | Kanegafuchi Chem Ind Co Ltd | Polyamic acid copolymer, polyimide copolymer consisting of the same copolymer and polyimide film and production thereof |
| US5166292A (en) * | 1991-10-29 | 1992-11-24 | E. I. Du Pont De Nemours And Company | Process for preparing a polyimide film with a preselected value for CTE |
| JP2004087548A (en) * | 2002-08-23 | 2004-03-18 | Kanegafuchi Chem Ind Co Ltd | Method for manufacturing printed wiring board |
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